X anions

A11R2X (much the most stable) X = anionic ligand especially Br ... 

Two types of chemical bonds, ionic and covalent, are found in chemical compounds. An ionic bond results from the transfer of valence electrons from the atom of an electropositive element (M) to the atom(s) of an electronegative element (X). It is due to coulombic (electrostatic) attraction between the oppositely charged ions, M (cation) and X (anion). Such ionic bonds are typical of the stable salts formed by combination of the metallic elements (Na, K, Li, Mg, etc.) with the nonmetallic elements (F, Cl, Br, etc.). As an example, the formation of the magnesium chloride molecule from its elemental atoms is shown by the following sequence ... 

Shown below is a representation of the ionic solid MX, where M cations are represented by squares and X anions are represented by circles. Fill in the box after the arrow to represent what happens to the solid after it has been completely dissolved in water. For simplicity, do not represent the water molecules. 

The first step consists in the attack of a proton on the W-H bond to yield a labile dihydrogen intermediate (Eq. (3)) that rapidly releases H2 to form a coordi-natively unsaturated complex (Eq. (4)). This complex adds water in the next step to form an aqua complex (Eq. (5)) that completes the reaction by substituting the coordinated water by the X anion (Eq. (6)). Steps (3)-(6) are repeated for each W-H bond and the factor of 3 in the rate constants appears as a consequence of the statistical kinetics at the three metal centers. The rate constants for both the initial attack by the acid (ki) and water attack to the coordinatively unsaturated intermediate (k2) are faster in the sulfur complex, whereas the substitution of coordinated water (k3) is faster for the selenium compound. 

These, then, cire the set of possible defects for the Plane Net, and the following summarizes the types of intrinsic defects expected. Note that we have used the labelling V = vacancy i = interstitial M = cation site X = anion site and s = surface site. We have already stated that surface sites are special. Hence, they are included in our listing of intrinsic defects. 

The Gibbs energy of an electroneutral system is independent of the electrostatic potential. In fact, when substituting into Eq. (3.7) the electrochemical potentials of the ions contained in the system and allowing for the electroneutrality condition, we can readily see that the sum of aU terms jZjF f is zero. The same is true for any electroneutral subsystem consisting of the two sorts of ion and (particularly when these are produced by dissociation of a molecule of the original compound k into x+ cations and x anions), for which... 

For compounds of the composition MX (M = cation, X = anion) the CsCl type has the largest Madelung constant. In this structure type a Cs+ ion is in contact with eight Cl-ions in a cubic arrangement (Fig. 7.1). The Cl- ions have no contact with one another. With cations smaller than Cs+ the Cl- ions come closer together and when the radius ratio has the value of rM/rx = 0.732, the Cl- ions are in contact with each other. When rM/rx < 0.732, the Cl- ions remain in contact, but there is no more contact between anions and cations. Now another structure type is favored its Madelung constant is indeed smaller, but it again allows contact of cations with anions. This is achieved by the smaller coordination number 6 of the ions that is fulfilled in the NaCl type (Fig. 7.1). When the radius ratio becomes even smaller, the zinc blende (sphalerite) or the wurtzite type should occur, in which the ions only have the coordination number 4 (Fig. 7.1 zinc blende and wurtzite are two modifications of ZnS). 

Five-coordinate Ni111 complexes (89) have been prepared by oxidation of the square planar Ni11 precursor complexes [Ni(L)X] with either X2 or CuX2, and the crystal structure of the iodo derivative has been determined. The geometry at Ni is best described as square pyramidal, with the Ni atom displaced approximately 0.34 A out of the basal plane towards the apical I atom. EPR confirms the Ni111 oxidation state, in which the unpaired electron of the low-spin d1 system is situated in the dz2 orbital.308,309 In aqueous solution full dissociation of both X anions occurs, while in acetone solution dissociation is not significant. The redox couple [Nin NCN (H20)]+/ [Ni111 NCN (H20)ra]2+ in water is +0.14V (vs. SCE). 

It is not clear whether the X anion remains ligated to the palladium(II) center. For example, for acetic acid, the palladium hydride was initially postulated as being HPd(OAc)L ,377,378 but more recently as HPdL +.367 To date, none of these complexes has been characterized.367 Oxidative addition of acetic acid or formic acid to a palladium(O) complex in DMF affords a cationic palladium hydride /ruw.v-I IPd(PPh3)2(DMF)+, with an acetate or a formate counter-anion. Both reactions are reversible and involve an unfavorable equilibrium so that a large excess of acid is required for the quantitative formation of the palladium hydride complex.379 This allows us to conclude that the catalytic reactions initiated by reaction of palladium(O) and acetic acid (or formic acid) proceed via a cationic palladium hydride trans-HPdfPPtHWDMF)"1", when they are performed in DMF.379... 

Most compounds R3EX can be described as essentially ionic, exhibiting structures that exhibit directed n(halide) - a (E- C) contacts between pyramidal R3E+ cations and X- anions.3... 

Examples of w-allylnickel-X compounds (X = anionic ligand) other than 77-allylnickel halides which have been used in combination with (alkyl)aluminum halides as olefin oligomerization catalysts are 7r-allyl-nickel acetylacetonate (11) (Section III), 7r-allylnickel aziridide (4, 56), and bis(7r-allyl)nickel (6) (59). In addition to ir-allylnickel halides, organo-nickel halides such as tritylnickel chloride (60, 61) and pentafluoro-phenylbis(triphenylphosphine)nickel bromide (62), or hydridonickel halides, e.g., trans-hydridobis(triisopropylphosphine)nickel chloride (12) (Section III), give active catalysts after activation with aluminum halides... 

Many uranium(VI) sulfoxide complexes of the type [U02X2(Me2S0)B] (X = anionic ligand) have been synthesized, including chloride, bromide (322, 323), nitrate (41), and acetate (431) adducts. The thiocyanate (113,114) and selenocyanate (292) adducts [U02(XCN)2(Me2SO)2] have been synthesized, and infrared data indicate the presence of O-Me2SO and JV-NCX ligands. 

Table 2 Systems within which structural data are available. All structurally characterised complexes have the formulation [Cu(L1))2]X2 (X=anion) with the exception of [Cu(LHe)2]Cl2 2H20, [Cu(Lmm)J Br2-2MeOH, [Cu(Lme)2][EtOSO3]033[HOSO3]067-0.33Et2O, [Cu(Lee)2]Cl2-H20, [Cu(Lee)2] Br2-MeOH, [Cu(Lbm)2]Cl2-2MeOH, [Cu(Lbm)2(0N02)]-[Cu(Lbm)2(0HMe)]-3N03-Et20...

Fig. 9-12. Simultaneous transfer of cations and anions at a semioon ductor electrode of ionic compound MX = cation X " = anion.

Similar bridge-splitting processes have been independently used to prepare the new cationic series trans-[PtX(CO)L2]BF4 (X = anions L = PEt3, PPhj, or PMe Ph), and cis-[PtClYLj (Y = SCN, NO3, or NOj). The geometries were suggested from their n.m.r. spectra. A detailed study was made of the effect of the trans influence of X on the reactivity of the trans-[PtX(CO)L2]BF4 complexes. 

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